JP2010006982A - Photosensitive polyorganosiloxane composition, polyorganosiloxane-cured relief pattern and method for forming the same, and semiconductor device and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive polyorganosiloxane composition which has excellent wettability when applied onto an organic thin film, excellent photosensitive properties when received UV-i light and excellent adhesiveness to the organic thin film and which is curable at low temperature, and to provide a polyorganosiloxane-cured relief pattern formed by using the photosensitive polyorganosiloxane composition, a method for forming the polyorganosiloxane-cured relief pattern, a semiconductor device and a method for producing the semiconductor device. <P>SOLUTION: The photosensitive polyorganosiloxane composition includes (a) 100 parts mass polysiloxane obtained by polymerizing a silanol compound having a specific structure and an alkoxysilane compound having another specific structure in the presence of a catalyst without adding water, (b) 0.2-20 parts mass photopolymerization initiator, (c) 0.01-10 parts mass nonionic surfactant and (d) 10-150 parts mass at least one organic solvent selected from compounds each having an alcoholic hydroxy group and ketone compounds. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to the formation of surface protection films, interlayer insulation films, α-ray shielding films, etc. in insulating materials for electronic components and semiconductor devices, and photosensitivity used in semiconductor devices equipped with image sensors, micromachines, or microactuators. The present invention relates to a resin composition and a semiconductor device manufactured using the resin composition.

Patent Document 1 discloses a photosensitive polyorganosiloxane composition as a coating material that has good storage stability, can be cured with ultraviolet rays, has high permeability, and can have a thickness of 1 to 150 μm. Specifically, ORMOCER ONE, a coating material made by Fraunhofer ISC, Germany, which consists of an organosilane having a polymerizable group and an organosilane having a hydrolysis reaction point using Ba (OH) ₂ (barium hydroxide) as a catalyst. There is. ORMOCER ONE can be cured at a low temperature of 150 ° C., and its cured product has excellent properties such as heat resistance of 300 ° C. or higher, residual low stress of 10 MPa or lower, flatness within 3%, and the like.

  However, only the technique disclosed in Patent Document 1 uses a photosensitive polyorganosiloxane composition as a permanent material such as a surface protective film, an interlayer insulating film, an α-ray shielding film, a partition, or a planarization film of an electronic component or a semiconductor device. It is difficult to achieve physical performances such as, for example, adhesion to a base material and mechanical properties at a practical level.

  On the other hand, a semiconductor device in which an element having an optical function or a mechanical function is mounted in an integrated circuit or separately from it is put into practical use. In many of these, after forming an element such as a transistor on a crystal substrate such as silicon using a conventionally known semiconductor process, an element having a function corresponding to the purpose of the semiconductor device is formed, and these are integrated into a package. It is manufactured by doing.

  As an example of such a packaging technique, for example, Patent Document 2 discloses a microstructure formed on a crystal substrate on which an integrated circuit is formed, a package material for covering the microstructure, and the package material. A semiconductor device having a spacer for supporting the microstructure and an example thereof are disclosed in detail. The technology disclosed in Patent Document 2 can be suitably used for various sensors such as microlens arrays and chemical sensors, or a wide range of semiconductor devices such as surface acoustic wave devices, but the invention described in Patent Document 2 is used. For implementation, a spacer for supporting the packaging material on the microstructure plays an important role. The following four points can be considered as characteristics required for the spacer.

  First, since this spacer should be formed only in a portion necessary as a support, it is advantageous that the spacer itself is formed of a photosensitive member. This is because, if the spacer itself has photosensitivity, the latter can be omitted from the lithography process and the etching process that are usually used to leave the spacer only in a necessary portion.

Secondly, the surface on which the spacer is formed is not necessarily composed of an inorganic material such as silicon, and a color filter layer, a protective film thereof, and other organic thin films may be formed. Therefore, the lithographic properties on these organic thin films must also be excellent.
One of the items that require lithographic properties is removability of the composition of the outer edge portion (edge) of a substrate such as a silicon wafer during coating. In the spacer manufacturing process, the silicon wafer is transported by a dedicated arm. At this time, if the composition remains on the outer edge of the silicon wafer, there is a problem that the device for manufacturing the spacer is contaminated. Therefore, in this step, a step (edge cut) of removing the composition on the outer edge of the silicon wafer is performed.

  A typical edge cutting method is a method of performing edge rinsing of the outer edge portion in the spin coating step and then drying with a hot plate. However, in this method, especially when the substrate is an organic thin film or the like, the phenomenon of the composition retreating from the outer edge of the substrate toward the center often occurs during the drying on the hot plate. Will cause trouble. In order to prevent this, good wettability on the organic thin film is required.

  Third, a member having low heat resistance, such as an adhesive such as an epoxy resin, is used around the spacer, and a microstructure located below the spacer does not necessarily have high heat resistance. Therefore, it can be said that the process for forming the spacer is more preferable as the temperature is lower.

  Although it is considered that the above-described characteristics are required for the spacer, Patent Document 2 does not disclose a specific member suitably used for the spacer.

EP 1196478 Special table 2003-516634 gazette

  The object of the present invention is to form a surface protection film, an interlayer insulation film, an α-ray shielding film, etc. in an insulating material of an electronic component or a semiconductor device in recent years, and a semiconductor device mounted with an image sensor, micromachine, or microactuator. Excellent photosensitive resin composition, that is, wettability at the time of coating on an organic thin film, photosensitive property in UV-i rays, that is, excellent pattern swelling and adhesion to a substrate, for example, 250 ° C. An object of the present invention is to provide a photosensitive polyorganosiloxane composition which can be cured at a low temperature as follows.

  The present invention is as follows.

[1] The following components (a) to (d),
(A) At least one selected from the group consisting of at least one silanol compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula (3) 100 parts by mass of a polyorganosiloxane obtained by polymerizing the alkoxysilane compound in the presence of a catalyst without adding water

(The plurality of R ₁ are each independently a group having 6 to 20 carbon atoms and containing at least one aromatic group.)

(R ₂ is an organic group having 2 to 17 carbon atoms including a group having a radical polymerizable carbon-carbon double bond, and the plurality of R ₃ are each independently a methyl group or an ethyl group.)

(R ₄ is an organic group having 2 to 17 carbon atoms which does not include a group having a radically polymerizable carbon-carbon double bond and includes at least one group having a 5- to 6-membered nitrogen atom-containing heterocyclic ring. And a plurality of R ₅ are each independently a methyl group or an ethyl group).
(B) 0.2-20 parts by mass of a photopolymerization initiator,
(C) 0.01-10 parts by mass of a nonionic surfactant, and (d) a photosensitive polysiloxane containing 10-150 parts by mass of at least one organic solvent selected from a compound having an alcoholic hydroxyl group and a ketone compound. Organosiloxane composition.

  [2] The photosensitive polyorganosiloxane composition according to [1], wherein the component (c) contains at least one fluorine atom.

  [3] The component (c) is represented by the following general formula (4)

(R ₆ is a trifluoromethyl group or a pentafluoroethyl group, and n is an integer of 1 to 25.)
The photosensitive polyorganosiloxane composition according to the above [1], which is at least one compound represented by the formula:

[4] A method for forming a polyorganosiloxane cured relief pattern using the photosensitive polyorganosiloxane composition according to any one of [1] to [3],
Applying the photosensitive polyorganosiloxane composition on a substrate to form a coating film;
Irradiating the coating film with an actinic ray through a patterning mask and photocuring the exposed portion;
Removing a portion other than the exposed portion of the coating film using a developer;
A method comprising heating at least the coating film and heat-curing the coating film;

  [5] A polyorganosiloxane cured relief pattern obtained by the method according to [4] above.

  [6] A semiconductor device comprising the polyorganosiloxane cured relief pattern according to [5].

[7] Crystal substrate on which an integrated circuit is formed, a microstructure formed on the crystal substrate, a package material for covering the microstructure, and the package material supported on the microstructure And a spacer material for
The semiconductor device according to [5] above, wherein the polyorganosiloxane cured relief pattern is formed as the spacer material.

  [8] The semiconductor device according to [7], wherein the integrated circuit includes a photodiode.

  [9] The semiconductor device according to [7], wherein the microstructure is a microlens.

[10] A method for producing a semiconductor device using the photosensitive polyorganosiloxane composition according to any one of [1] to [3],
A step of coating the photosensitive polyorganosiloxane composition directly or via a thin film layer on a microstructure formed on a crystal substrate on which an integrated circuit is formed, to form a coating film;
Irradiating the coating film with an actinic ray through a patterning mask and photocuring the exposed portion;
Removing a portion other than the exposed portion of the coating film using a developer;
A method comprising heating at least the coating film and heat-curing the coating film;

  According to the present invention, a photosensitive polyorgano excellent in wettability at the time of coating on an organic thin film, photosensitive property with UV-i rays and adhesion to an organic thin film, and capable of being cured at a low temperature of, for example, 250 ° C. or lower. A siloxane composition is provided, and a polyorganosiloxane cured relief pattern and a semiconductor device including the same are provided.

  Examples of typical embodiments of the present invention will be specifically described below.

<Photosensitive polyorganosiloxane composition>
(A) Polyorganosiloxane The polyorganosiloxane used in the photosensitive polyorganosiloxane composition of the present invention is represented by at least one silanol compound represented by the following general formula (1) and the following general formula (2). A compound and at least one alkoxysilane compound selected from the group consisting of compounds represented by the following general formula (3) are mixed and polymerized without adding water in the presence of a catalyst.

(The plurality of R ₁ are each independently a group having 6 to 20 carbon atoms and containing at least one aromatic group.)

(R ₂ is an organic group having 2 to 17 carbon atoms including a group having a radical polymerizable carbon-carbon double bond, and the plurality of R ₃ are each independently a methyl group or an ethyl group.)

(R ₄ is an organic group having 2 to 17 carbon atoms which does not include a group having a radically polymerizable carbon-carbon double bond and includes at least one group having a 5- to 6-membered nitrogen atom-containing heterocyclic ring. And a plurality of R ₅ are each independently a methyl group or an ethyl group.)
Here, the nitrogen atom-containing heterocycle may or may not have aromaticity.

In at least one silanol compound represented by the above general formula (1) (hereinafter simply referred to as “silanol compound” unless otherwise specified), R ₁ represents the number of carbon atoms containing at least one aromatic group. 6 to 20 groups. Specifically, R ₁ is preferably at least one group selected from the groups represented by the following structures.

(A is one kind of group selected alkyl group of 1 to 4 carbon atoms, from the group consisting of _{-CH = CH 2, -CH = CH} -CH 3 and -CH ₂ -CH = CH _2, y is 0 1 or an integer of 2)

  Examples of suitable silanol compounds include diphenylsilane diol, di-p-toluylsilane diol, di-p-styrylsilane diol, and dinaphthylsilane diol. In view of price, availability, performance and the like, diphenylsilanediol is particularly suitable.

In the compound represented by the general formula (2), R ₂ is an organic group having 2 to 17 carbon atoms including a group having a radical polymerizable carbon-carbon double bond. Several R < ₃ > is a methyl group or an ethyl group each independently.

The group having a radical polymerizable carbon-carbon double bond represented by R ₂ is preferably at least one group selected from the groups represented by the following structures.

(D is one group selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, and z is an integer of 0, 1 or 2.)

  Suitable examples of the compound represented by the general formula (2) include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 1-propenyltrimethoxysilane, 1-propenyltriethoxysilane, 2-propenyltrimethoxysilane, 2-propenyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, p- (1-propenylphenyl) trimethoxysilane, p- (1-propenylphenyl) triethoxysilane, p- (2-propenylphenyl) trimethoxysilane, - (2-propenyl-phenyl) triethoxysilane and the like. In order to obtain excellent photosensitivity, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, and 3-acryloyloxypropyltriethoxysilane are more preferable. And 3-methacryloyloxypropyltrimethoxysilane is particularly preferable in view of toxicity, toxicity and performance.

In the compound represented by the general formula (3), R ₄ does not include a radically polymerizable group having a carbon-carbon double bond, and has a 5- to 6-membered nitrogen atom-containing heterocyclic ring (has aromaticity). A plurality of R _{5 s} are each independently a methyl group or an ethyl group.

Specific examples of the radicals containing a radically polymerizable carbon-carbon double bond represented by R ₄ and a 5- to 6-membered nitrogen atom-containing heterocyclic ring (including those having no aromaticity) are also included. Is preferably a group represented by the following structure.

(B is one group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 3 carbon atoms, and p is 0 or an integer of 1 to 3)

  Examples of the compound represented by the general formula (3) (hereinafter, the alkoxy moiety represents a methoxy group or an ethoxy group) include N-trialkoxysilyl-1,2,4-triazole, N-trialkoxysilyl. Imidazole, N-trialkoxysilylpyrrole, N-trialkoxysilylpyridine, N-trialkoxysilylpyrrolidine, piperidinomethyltrialkoxysilane, 2-piperidinoethyltrialkoxysilane, 3-piperidinopropyltrialkoxysilane , (4-methylpiperidinopropyl) trialkoxysilane, 3-morpholinopropyltrialkoxysilane, 3-piperazinopropyltrialkoxysilane, 3- (4-methylpiperazinopropyl) trialkoxysilane, 2- ( 4-pyridylethyl) trialkoxy Silane, N-(3- trialkoxysilylpropyl) -4,5-dihydroimidazole, N-(3- trialkoxysilylpropyl) pyrrole, and the like.

  When the compound represented by the general formula (3) is used as a part of the raw material of the polyorganosiloxane, the tackiness (stickiness) of the soft baked film (that is, the film after pre-baking) of the photosensitive polyorganosiloxane composition using the compound is used. Sense) improved dramatically. Among them, 3-morpholinopropyltrialkoxysilane, 3-piperazinopropyltrialkoxysilane, 3-piperidinopropyltrialkoxysilane, 2- (trialkoxysilylethyl) pyridine, 2- (4-pyridylethyl) trialkoxy It is particularly preferable to use silane (the alkoxy moiety represents a methoxy group or an ethoxy group).

  (A) When polymerizing polyorganosiloxane, at least one silanol compound represented by the above general formula (1), a compound represented by the above general formula (2), and the above general formula (3) are represented. And at least one alkoxysilane compound selected from the group consisting of compounds (hereinafter simply referred to as “alkoxysilane compound” means the above alkoxysilane compound) at a molar ratio of 1: 1. Is the basis. Further, as the alkoxysilane compound, at least one alkoxysilane compound selected from the group consisting of compounds represented by the general formula (2) may be used alone, or may be represented by the general formula (3) as desired. Use of at least one alkoxysilane compound selected from the group consisting of compounds represented by the above general formula (2) is also possible by using a mixture with at least one alkoxysilane compound selected from the group consisting of the above compounds. The molar ratio is preferably 30 to 100 mol% of all alkoxysilane compounds. When the molar ratio of the at least one alkoxysilane compound selected from the group consisting of the compound represented by the general formula (2) is 30 mol% or more of the total alkoxysilane compounds, the photosensitive polyorganosiloxane composition is particularly suitable. Excellent photosensitive properties can be imparted.

  In the present invention, the polymerization of the silanol compound and the alkoxysilane compound is carried out in the presence of a catalyst without actively adding water. The catalyst is selected from the group consisting of a silanol group of at least one silanol compound represented by the general formula (1), a compound represented by the general formula (2), and a compound represented by the general formula (3). A compound that promotes the dealcoholization condensation reaction with the alkoxysilyl group of at least one alkoxysilane compound can be used. As a suitable catalyst, at least one metal alkoxide selected from the group consisting of a compound represented by the following general formula (5) and a compound represented by the following general formula (6) (hereinafter simply referred to as “metal alkoxide”) And at least one compound selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides.

(M ₁ represents one element selected from the group consisting of silicon, germanium, titanium, and zirconium, and R ₇ is one group selected from the group consisting of alkyl groups having 1 to 4 carbon atoms.)

(M ₂ represents boron or aluminum, and R ₈ represents one group selected from the group consisting of alkyl groups having 1 to 4 carbon atoms.)

  The metal alkoxide represented by the general formula (5) and the general formula (6) includes the silanol group of the silanol compound represented by the general formula (1), the compound represented by the general formula (2), and the general formula. While catalyzing the dealcoholization condensation reaction of the alkoxysilyl group of at least one alkoxysilane compound selected from the group consisting of the compounds represented by (3), it itself behaves as an alkoxy group-containing compound and participates in the dealcoholization condensation reaction. A part of which is incorporated into the polyorganosiloxane.

  The mixing ratio of the metal alkoxide is based on mixing the silanol compound and the alkoxysilane compound 1: 1, and when mixing the metal alkoxide here, a part of the alkoxysilane compound is replaced (the alkoxysilane compound mixing amount is changed). It is preferable to adjust the overall mixing ratio in the form of a constant ratio.

  Specifically, when the tetravalent metal alkoxide represented by the above general formula (5) is used as the metal alkoxide, the tetravalent metal alkoxide and the alkoxysilane compound are respectively converted at a molar ratio of 1: 2. It is preferable to replace (the amount of alkoxysilane compound is reduced by 2 mol for every 1 mol of the amount of tetravalent metal alkoxide mixed). When the trivalent metal alkoxide represented by the general formula (6) is used, the trivalent metal alkoxide and the alkoxysilane compound are preferably converted at a molar ratio of 2: 3 and replaced.

  Moreover, as a suitable trivalent or tetravalent metal alkoxide represented by the general formula (5) or the general formula (6), trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, tri-iso -Propoxyaluminum, tri-n-butoxyaluminum, tri-iso-butoxyaluminum, tri-sec-butoxyaluminum, tri-tert-butoxyaluminum, trimethoxyboron, triethoxyboron, tri-n-propoxyboron, tri-iso -Propoxyboron, tri-n-butoxyboron, tri-iso-butoxyboron, tri-sec-butoxyboron, tri-tert-butoxyboron tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i o-propoxysilane, tetra-n-butoxysilane, tetra-iso-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetramethoxygermanium, tetraethoxygermanium, tetra-n-propoxygermanium, tetra- iso-propoxygermanium, tetra-n-butoxygermanium, tetra-iso-butoxygermanium, tetra-sec-butoxygermanium, tetra-tert-butoxygermanium, tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetra- iso-propoxy titanium, tetra-n-butoxy titanium, tetra-iso-butoxy titanium, tetra-sec-butoxy titanium, tetra-tert-butoxy titanium, Tramethoxyzirconium, tetraethoxyzirconium, tetra-n-propoxyzirconium, tetra-iso-propoxyzirconium, tetra-n-butoxyzirconium, tetra-iso-butoxyzirconium, tetra-sec-butoxyzirconium, tetra-tert-butoxyzirconium Can be mentioned. In order to achieve a rapid and uniform polymerization reaction, those which are liquid in the reaction temperature range are preferable, and tetra-iso-propoxytitanium is particularly preferable in view of high activity as a catalyst and availability. .

  The heating temperature for polymerizing the polyorganosiloxane is an important parameter for controlling the degree of polymerization of the polyorganosiloxane produced. Although depending on the desired degree of polymerization, it is preferable to polymerize by heating the mixture of the raw materials described above to about 70 ° C to 150 ° C.

  With respect to the silanol compound represented by the general formula (1), when the addition amount during the polymerization of the metal alkoxide is less than 2 mol%, the degree of polymerization of the polyorganosiloxane can be increased even when heated above the preferred temperature range. It tends to be difficult to raise as expected. In such a case, when an appropriate amount of alkali metal hydroxide or alkaline earth metal hydroxide is added as a catalyst, the shortage of metal alkoxide can be compensated and the degree of polymerization of the resulting polyorganosiloxane can be controlled appropriately. It becomes.

  Suitable alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like. Suitable alkaline earth metal hydroxides include alkaline earth metal hydroxides such as calcium hydroxide, strontium hydroxide and barium hydroxide, and hydrates thereof.

  The preferable upper limit of the polymerization addition amount of the metal alkoxide depends on the performance of the target polyorganosiloxane. In order to achieve excellent photosensitivity, the alkoxysilane compound preferably has a photopolymerizable carbon-carbon double bond. Considering the desired amount of the photopolymerizable carbon-carbon double bond, the upper limit of the polymerization amount of the metal alkoxide is preferably 40 mol% or less with respect to the silanol compound represented by the general formula (1). Preferably it is 30 mol% or less.

(B) Photopolymerization initiator It is necessary to add a photopolymerization initiator to the photosensitive polyorganosiloxane composition of the present invention for the purpose of imparting photosensitivity. Preferable compounds include the following compounds.

  (1) Benzophenone derivatives: for example, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone.

  (2) Acetophenone derivatives: for example, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl Ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl)- [Benzyl] -phenyl} -2-methylpropan-1-one, methyl phenylglyoxylate.

  (3) Thioxanthone derivatives: For example, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone.

  (4) Benzyl derivatives: for example, benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal.

  (5) Benzoin derivatives: for example, benzoin, benzoin methyl ether, 2-hydroxy-2-methyl-1-phenylpropan-1-one.

  (6) Oxime compounds: for example, 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanetrione-2 -(O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O- Benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O Acetyl oxime).

  (7) α-hydroxy ketone compounds: for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl -1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropane.

  (8) α-aminoalkylphenone compounds: for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methylbenzyl)- 1- (4-Morpholin-4-yl-phenyl) butan-1-one.

  (9) Phosphine oxide compounds: for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

(10) Titanocene compound: for example, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium.

  Moreover, in using these, it may be individual or a mixture of 2 or more types.

  Among the photopolymerization initiators described above, the α-aminoalkylphenone compound (8) is more preferable particularly from the viewpoint of photosensitivity. In this invention, the addition amount of the photoinitiator which is (b) component is 0.2-20 mass parts with respect to 100 mass parts of polyorganosiloxane which is (a) component, and 1-10 mass parts Is more preferable. If the addition amount is 0.2 parts by mass or more, radicals sufficient to allow radical photopolymerization to proceed sufficiently are supplied during exposure, so that curing of the exposed part proceeds to obtain a practical relief pattern. Can do. On the other hand, if the addition amount is 20 parts by mass or less, the exposure light beam reaches near the substrate surface in order to prevent the exposure absorption near the coating film surface from becoming too large. Can be obtained uniformly and a practical relief pattern can be obtained.

(C) Nonionic surfactant A nonionic surfactant is added to the photosensitive polyorganosiloxane composition of the present invention for the purpose of improving the wettability with respect to various substrates represented by organic thin films. is required. There are two types of surfactants: ionic surfactants that dissociate into ions and nonionic surfactants that do not dissociate, but ionic surfactants often contain metal corrosive ionic components. When this is added to the photosensitive polyorganosiloxane composition of the present invention, there is a high possibility that after the formation of the semiconductor device, the residual ion component causes a malfunction due to corrosion or dielectric breakdown of metal wiring or the like. Therefore, in the photosensitive polyorganosiloxane composition of the present invention, it is important to select a nonionic surfactant that contains as little ionic components as possible.

  Preferred nonionic surfactants include the following compounds.

  [1] Ether type surfactant: For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polycyclic phenyl ether, polyoxypropylene alkyl ether.

  [2] Ester ether type surfactant: For example, polyoxyethylene glyceryl ether fatty acid ester, polyoxyethylene hydrogenated castor oil fatty acid ester.

  [3] Ester type surfactant: For example, polyethylene glycol fatty acid ester, polyoxyethylene trimethylolpropane fatty acid ester.

  [4] Silicone surfactant: For example, dimethylsiloxane ethyleneoxy graft compound, dimethylsiloxane propyleneoxy graft compound, (hydroxyethyleneoxypropyl) methylsiloxane-dimethylsiloxane compound.

  [5] Fluorosurfactant: For example, at least one compound selected from the group consisting of perfluoroalkylcarboxylic acid, perfluoroalkylsulfonic acid, and the following general formula (4).

(R ₆ is a trifluoromethyl group or a pentafluoroethyl group, and n is an integer of 1 to 25.)

  In using these, it may be individual or a mixture of two or more.

Among the above-mentioned (c) nonionic surfactants, the fluorine surfactant of the above [5] is more preferable from the viewpoint of improving the wettability with respect to the organic thin film. In particular, the compound represented by the general formula (4) is more preferable because it does not contain a perfluoroalkyl group (C _n F _{2n + 1} , n = 6 to 12), which has been pointed out to be harmful to the environment. In this invention, the addition amount of the nonionic surfactant which is (c) component is 0.01-10 mass parts with respect to 100 mass parts of polyorganosiloxane which is (a) component, It is more preferable to set it to -5 mass parts.

  If the addition amount is 0.01 parts by mass or more, the wettability with respect to the organic thin film is improved. On the other hand, if the addition amount is 10 parts by mass or less, it is possible to suppress development portion residue, pattern lifting and peeling in lithography.

(D) Alcohol-based and ketone-based organic solvents The photosensitive polyorganosiloxane composition of the present invention is selected from a compound having an alcoholic hydroxyl group and a ketone compound for the purpose of improving wettability on an organic thin film. It is necessary to add at least one organic solvent.

  As the compound having an alcoholic hydroxyl group, aromatic, aliphatic and alicyclic alcohols, glycols and derivatives thereof are preferably used. As the ketone compound, aromatic, aliphatic, and alicyclic monoketones and diketones are preferably used. Specific examples include the following compounds.

(1) Aliphatic alcohol: for example
Methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, 1-pentanol, isoamyl alcohol, s-amyl alcohol, t-amyl alcohol, 2-methyl- 1-butanol, 1-hexanol, 2-ethyl-1-butanol, 4-methyl-2-pentanol, isohexyl alcohol, methyl-1-pentanol, s-hexanol, 1-heptanol, isoheptyl alcohol, 2, 3-dimethyl-1-pentanol, 1-octanol, 2-ethylhexanol, isooctyl alcohol, 2-octanol, 3-octanol, 1-nonanol, isononyl alcohol, 3,5,5-trimethylhexanol, 1-decanol Isodecyl alcohol, 3,7-dimethyl-1-octanol, 1-Hendekanoru, 1-dodecanol, isododecyl alcohol, allyl alcohol, propargyl alcohol, Hekishinoru.

(2) Aromatic alcohol: for example
Benzyl alcohol, (2-hydroxyphenyl) methanol, (methoxyphenyl) methanol, (3,4-dihydroxyphenyl) methanol, 4- (hydroxymethyl) benzene-1,2-diol, (4-hydroxy-3-methoxyphenyl) ) Methanol, (3,4-dimethoxyphenyl) methanol, (4-isopropylphenyl) methanol, 2-phenylethanol, 1-phenylethanol, 2-phenyl-1-propanol, p-tolyl alcohol, 2- (4-hydroxy) -3-methoxyphenyl) ethane-1-ol, 2- (3,4-dimethoxyphenyl) ethane-1-ol, 3-phenylpropan-1-ol, 2-phenylpropan-2-ol, cinnamyl alcohol, 3- (4-Hydroxy-3-methoxyph Nyl) prop-2-en-1-ol, 3- (4-hydroxy-3,5-methoxyphenyl) prop-2-en-1-ol, diphenylmethanol, trityl alcohol, 1,2-diphenylethane-1 , 2-diol, 1,1,2,2, -tetraphenylethane-1,2-diol, benzene-1,2-dimethanol, benzene-1,3-dimethanol, benzene-1,4-dimethanol .

(3) Alicyclic alcohol: for example
Cyclohexanol, methylcyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, tetrahydro-2-furanmethanol.

(4) Glycol and its derivatives: for example
Ethylene glycol, ethylene glycol monoalkyl (C = 1-8) ether, ethylene glycol monovinyl ether, ethylene glycol monophenyl ether, dioxane, diethylene glycol monoalkyl (C = 1-6) ether, diethylene glycol monovinyl ether, diethylene glycol monophenyl ether, Triethylene glycol monoalkyl (C = 1-3) ether, triethylene glycol monovinyl ether, triethylene glycol monophenyl ether, tetraethylene glycol monophenyl ether, propylene glycol, propylene glycol monoalkyl (C = 1-4) ether, Propylene glycol monophenyl ether, dipropylene glycol monoalkyl (C = 1-3) ether , Ethylene glycol monoacetate, propylene glycol monoacrylate, propylene glycol monoacetate.

(5) Ketone compounds: for example
Acetone, methyl ethyl ketone, 3-butyn-2-one, methyl-n-propyl ketone, methyl isopropyl ketone, 3-pentyn-2-one, methyl isopropenyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, mesityl oxide, 4-hydroxy-4-methyl-2-pentanone, methyl-n-amyl ketone, methyl isoamyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, diisopropyl ketone, 2-octanone, 3-octanone, 5-methyl- 3-heptanone, 5-nonanone, diisobutylketone, trimethylnonanone, 2,4-pentanedione, 2,5-hexanedione, cyclopentanone, cyclohexanone, methylcyclohexanone, acetophenone, propiophenone, isophorone and the like.

Said suitable organic solvent may be used independently, or 2 or more types may be mixed and used for it.
Among the above-mentioned preferred organic solvents, iso-butyl alcohol is particularly preferable as an excellent derivation of the effect of the nonionic surfactant in the photosensitive polyorganosiloxane composition of the present invention, and at the same time, safe and easy to handle. , Benzyl alcohol, ethylene glycol monophenyl ether, methyl-n-amyl ketone, 2-octanone, and acetophenone are preferable.

  In this invention, the addition amount of the organic solvent which is (d) component is 10-150 mass parts with respect to 100 mass parts of polyorganosiloxane which is (a) component, and shall be 20-90 mass parts. More preferred. When the addition amount is 10 parts by mass or more, the effect of the nonionic surfactant is improved. In addition, if the addition amount is 150 parts by mass or less, a practically sufficient composition viscosity can be ensured even during thick film molding in the process of applying the composition on various substrates, resulting in in-plane uniformity. The coating film can be made excellent.

  The photosensitive polyorganosiloxane composition of the present invention contains a group having a photopolymerizable unsaturated bond in addition to the component (a) for the purpose of improving film-forming characteristics, photosensitive characteristics, and mechanical properties after curing. Compounds can be added. As such a compound, a polyfunctional (meth) acryl compound that can be polymerized by the action of a photopolymerization initiator is preferable. For example, polyethylene glycol diacrylate [number of ethylene glycol units 2 to 20], polyethylene glycol dimethacrylate [ethylene Number of glycol units 2-20], poly (1,2-propylene glycol) diacrylate [1,2-propylene glycol units number 2-20], poly (1,2-propylene glycol) dimethacrylate [1,2- Propylene glycol units 2 to 20], polytetramethylene glycol diacrylate [tetramethylene glycol units 2 to 10], polytetramethylene glycol dimethacrylate [tetramethylene glycol units 2 to 10], 1,4- Chlohexanediacrylate, 1,4-cyclohexanedimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate [number of ethylene glycol units 2 to 20], trimethylolpropane Trimethacrylate, tri-2-hydroxyethyl isocyanurate triacrylate, tri-2-hydroxyethyl isocyanurate trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, ditrimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate Dipentaerythritol hexaacrylate , Methylene bisacrylamide, ethylene glycol diglycidyl ether-methacrylic acid adduct, glycerol diglycidyl ether-acrylic acid adduct, bisphenol A diglycidyl ether-acrylic acid adduct, bisphenol A diglycidyl ether-methacrylic acid adduct, ethoxy Bisphenol A diacrylate [number 2-30 of ethylene glycol units], ethoxylated bisphenol A dimethacrylate [number 2-30 of ethylene glycol units], N, N′-bis (2-methacryloyloxyethyl) urea, etc. It is done. Moreover, in using these, you may use individually or in mixture of 2 or more types as needed. The addition amount in the case of adding these compounds is preferably 1 to 100 parts by mass and more preferably 5 to 50 parts by mass with respect to 100 parts by mass of component (a).

  A silicone resin can be added to the photosensitive polyorganosiloxane composition of the present invention for the purpose of improving the tackiness and fluidity of the coating film after soft baking. The silicone resin here is, for example, “organosilane compound having 2 to 4 hydrolyzable groups such as alkoxysilyl group and chlorosilyl group” described in “Silicone Handbook” (1990) published by Nikkan Kogyo Shimbun. It is a “polymer having a three-dimensional network structure obtained by cohydrolyzing and polymerizing”.

  In the object of the present invention, it is preferable to add a so-called straight silicone resin such as methyl, phenyl, phenylmethyl, phenylethyl, and phenylpropyl. Examples of these include methyl silicone resins such as KR220L, KR242A, KC89, KR400, and KR500 (manufactured by Shin-Etsu Chemical Co., Ltd.), 217 flakes (manufactured by Dow Corning Toray), SR-20, SR-21 (manufactured by Konishi Chemical Industries, Ltd.). Phenyl silicone resins such as KR213, KR9218 (manufactured by Shin-Etsu Chemical Co., Ltd.), 220 flakes, 223 flakes, 249 flakes (manufactured by Dow Corning Toray), SR-23 (Konishi Chemical) And the like, and phenylpropyl silicone resins such as Z-6018 (manufactured by Dow Corning Toray). For the purpose of improving tackiness and fluidity, it is preferable to add a silicone resin that has a higher crosslink density and is solid in a normal temperature range. In that sense, among the above preferred examples, a phenyl-based or phenylpropyl-based silicone resin is preferably used. It is particularly preferred to select. Furthermore, those having a silanol residue in a part of the structure are preferred because the inventors have clarified a tendency to further improve the tackiness and fluidity by examination.

  It is preferable that the addition amount of the said silicone resin suitable for this invention is 50-200 mass parts with respect to 100 mass parts of (a) component. In order to satisfactorily improve the tackiness and fluidity, the amount is preferably 50 parts by mass or more, and if it is 200 parts by mass or less, lithography properties such as i-line sensitivity can be maintained satisfactorily.

  A sensitizer for improving photosensitivity can be added to the photosensitive polyorganosiloxane composition as desired. Examples of such a sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzylidene) cyclopentanone, and 2,6-bis (4′-diethylamino). Benzylidene) cyclohexanone, 2,6-bis (4′-dimethylaminobenzylidene) -4-methylcyclohexanone, 2,6-bis (4′-diethylaminobenzylidene) -4-methylcyclohexanone, 4,4′-bis (dimethylamino) ) Chalcone, 4,4′-bis (diethylamino) chalcone, 2- (4′-dimethylaminocinnamylidene) indanone, 2- (4′-dimethylaminobenzylidene) indanone, 2- (p-4′-dimethylamino) Biphenyl) benzothiazole, 1,3-bis (4-dimethyla) Nobenzylidene) acetone, 1,3-bis (4-diethylaminobenzylidene) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7- Dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N-ethylethanolamine, N-phenyldiethanolamine N-p-tolyldiethanolamine, N-phenylethanolamine, N, N-bis (2-hydroxyethyl) aniline, 4-morpholinobenzophenone, isoamyl 4-dimethylaminobenzoate, 4-diethylamino Isoamyl benzoate, benztriazole, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, 1-cyclohexyl-5-mercapto-1,2,3,4-tetrazole, 1- (tert-butyl) -5-mercapto-1,2,3,4-tetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benz Examples include thiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-p) thiazole, 2- (p-dimethylaminobenzoyl) styrene, and the like. In use, it may be used alone or as a mixture of two or more. The addition amount in the case of adding the sensitizer is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (a), although there is a balance with other additive component amounts. More preferably, it is 5-5 mass parts.

  A polymerization inhibitor can be added to the photosensitive polyorganosiloxane composition of the present invention as desired for the purpose of improving the viscosity during storage and the stability of photosensitivity. Examples of such polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid. 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N- Ethyl-N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt ,Screw 4-hydroxy-3,5-di-tert- butyl) phenyl methane, or the like can be used. The addition amount in the case of adding a polymerization inhibitor is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of component (a).

A silane coupling agent can be added to the photosensitive polyorganosiloxane composition of the present invention for the purpose of further improving the adhesion to various substrates. Examples of the silane coupling agent include the following. (Hereinafter, the notation of alkoxy indicates a methoxy group or an ethoxy group.)
Vinyltrialkoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropylmethyldialkoxysilane, p-styryltrialkoxysilane, 3-methacryloxy Propyltrialkoxylane, 3-methacryloxypropylmethyl dialkoxylane, 3-acryloxypropyltrialkoxylane, 3-acryloxypropylmethyl dialkoxylane, N-2 (aminoethyl) -3-aminopropyltrialkoxysilane, N-2 (aminoethyl) -3-aminopropylmethyl dialkoxysilane, 3-aminopropyltrialkoxysilane, 3-trialkoxysilyl-N- (1.3-dimethyl-butylidene) propylamine, N-Fe -3-aminopropyltrialkoxysilane, 3-ureidopropyltrialkoxysilane, 3-ureidopropylmethyldialkoxysilane, 3-mercaptopropyltrialkoxysilane, 3-mercaptopropylmethyldialkoxysilane, bis (trialkoxysilylpropyl) ) Tetrasulfide, 3-isocyanatopropyltrialkoxysilane and the like.

  The addition amount of the silane coupling agent is preferably 0.1 to 50 parts by mass, more preferably 2 to 35 parts by mass with respect to 100 parts by mass of the component (a).

  In the photosensitive polyorganosiloxane composition of the present invention, an organic solvent other than the component (d) can be added to adjust the viscosity, and improve the uniformity and storage stability of the composition. Suitable solvents include N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, morpholine, N -Methylmorpholine, N-phenylmorpholine, morpholinoacetophenone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, propylene glycol monomethyl Examples include ether, propylene glycol monomethyl ether acetate, anisole, ethyl acetate, ethyl lactate, and butyl lactate, and these can be used alone or in combination of two or more.

  In addition to the above, the photosensitive polyorganosiloxane composition of the present invention includes an ultraviolet absorber and the like, as long as it does not inhibit various characteristics of the photosensitive polyorganosiloxane composition of the present invention. Various additives can be appropriately blended.

<Method for forming polyorganosiloxane cured relief pattern>
The present invention also provides a method for forming a polyorganosiloxane cured relief pattern using the photosensitive polyorganosiloxane composition described above. Typically, a polyorganosiloxane cured relief pattern is formed by applying a photosensitive polyorganosiloxane composition on a substrate to form a coating film, and applying an actinic ray to the coating film through a patterning mask. A step of irradiating and photocuring the exposed portion; a step of removing a portion other than the exposed portion of the coating film using a developer; and a step of heating and curing the coating film by heating at least the coating film. The above steps will be further described below.

[Process of forming a coating film by applying photosensitive polyorganosiloxane composition]
The photosensitive polyorganosiloxane composition of the present invention is applied onto various desired base materials such as a silicon wafer, a ceramic substrate, an aluminum substrate, and a substrate on which an organic thin film is formed to form a coating film. As the coating apparatus or coating method, a spin coater, a die coater, a spray coater, dipping, printing, a blade coater, roll coating, or the like can be used. After application, soft baking (pre-baking) may be performed at 80 to 200 ° C.

[Step of irradiating the coating film with an actinic ray through a patterning mask to photocure the exposed portion]
Using the desired patterning mask as a photomask, the coating film formed as described above is irradiated with actinic rays using an exposure projection apparatus such as a contact aligner, mirror projection, or stepper.

  X-rays, electron beams, ultraviolet rays, visible rays and the like can be used as the actinic rays, but in the present invention, those having a wavelength of 200 to 500 nm are preferably used. In light of pattern resolution and handleability, the light source wavelength of the actinic ray is particularly preferably UV-i rays (365 nm), and a stepper is particularly preferable as the exposure projection apparatus.

  Post exposure bake (PEB) by any combination of temperature and time (preferably temperature 40 ° C. to 200 ° C., time 10 seconds to 360 seconds), if necessary, for the purpose of improving photosensitivity after exposure, Baking before development may be performed.

[Step of removing a portion other than the exposed portion of the coating film using a developer]
Development with a developer can be performed by selecting from methods such as dipping, paddle, and rotary spraying. Thereby, an uncured portion of the coating film, that is, a portion other than the exposed portion is removed, and a relief pattern after development is obtained. As the developer, the good solvent of the photosensitive polyorganosiloxane composition of the present invention can be used alone, or a good solvent and a poor solvent can be appropriately mixed. Good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, α-acetyl-gammabutyrolactone, cyclo Pentanone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone, etc., as poor solvents, methanol, ethanol, iso-propanol, butanol, isobutanol, pentanol, Methyl isobutyl carbinol and water are used.

  After the development is completed, the film is washed with a rinse solution, and the developer solution is removed to obtain a coating film with a relief pattern. As the rinsing liquid, distilled water, methanol, ethanol, iso-propanol, propylene glycol monomethyl ether, iso-butyl alcohol, pentanol, methyl isobutyl carbinol, 4-methyl-1-pentanol or the like may be used alone or as appropriate mixed. They can also be used in combination in stages.

[Step of heating and curing at least the coating film]
The obtained post-development relief pattern is heat-cured at a curing temperature, for example, 150 to 250 ° C., which is much lower than before, and may be abbreviated as a polyorganosiloxane cured relief pattern (hereinafter referred to as a cured relief pattern). ). This heat curing can be performed using a hot plate, an inert oven, a temperature rising oven that can set a temperature program, or the like. Air may be used as the atmospheric gas for heat curing, and an inert gas such as nitrogen or argon may be used as necessary. As described above, a polyorganosiloxane cured relief pattern can be formed.

<Semiconductor device and manufacturing method thereof>
The present invention also provides a semiconductor device including the polyorganosiloxane cured relief pattern and a method for manufacturing the same. The polyorganosiloxane cured relief pattern described above is, for example, a surface protective film of a semiconductor device formed on a substrate such as a silicon wafer, an interlayer insulating film, an α-ray shielding film, or a microstructure such as a microlens array, It can be used as at least one of the support (partition wall) between the package material for covering the microstructure and the package material. In manufacturing a semiconductor device, processes other than the formation of the polyorganosiloxane cured pattern described above can apply a known semiconductor device manufacturing method, thereby manufacturing various semiconductor devices including optical elements such as CMOS image sensors. be able to. Moreover, the electronic component and semiconductor device which have the coating film which consists of resin which hardened the photosensitive polyorganosiloxane composition of this invention mentioned above can be obtained.

  The semiconductor device of the present invention includes a crystal substrate on which an integrated circuit is formed, a microstructure formed on the crystal substrate, a package material for covering the microstructure, and the package material as the microstructure. And a spacer material for supporting on the body. In this case, the polyorganosiloxane cured relief pattern of the present invention can be formed as the spacer material. Here, specific examples of the integrated circuit include a crystal substrate and a photodiode including silicon, lithium niobate, lithium tartrate, or quartz. A microstructure means a micron-sized mechanical, photomechanical, or electromechanical device. Specifically, a microlens is mentioned, for example. The packaging material is preferably transparent and may be formed of glass.

  As a manufacturing method of the semiconductor device, a process for forming the coating film by applying the photosensitive polyorganosiloxane composition of the present invention directly or through a thin film layer on a microstructure, and opening only a portion where a spacer material is to be formed. A step of irradiating the coating film with an actinic ray through a patterning mask having a portion to photocure the exposed portion, and removing a non-cured portion of the coating film using the developer, that is, a portion other than the exposed portion And a manufacturing method including at least a step of heating the coating film. Each step can be performed by the same method as described above.

  Next, the present invention will be further described with reference to examples and comparative examples.

[Synthesis Example 1]
(Synthesis of polyorganosiloxane P-1)
In a 2-liter round bottom flask equipped with a water-cooled condenser and a stirring blade with a vacuum seal, 540.78 g (2.5 mol) of diphenylsilanediol, 577.41 g (2.325 mol) of 3-methacryloyloxypropyltrimethoxysilane, tetra -24.87g (0.0875mol) of iso-propoxy titanium was prepared, and stirring was started. This was immersed in an oil bath, the heating temperature was set to 120 ° C., and heating was started from room temperature. On the way, methanol generated with the progress of the polymerization reaction was allowed to react with a water-cooled condenser while reacting until the temperature of the reaction solution became constant, and then heated and stirred for another 30 minutes.

  Then, attach a hose connected to a cold trap and a vacuum pump, stir vigorously while heating at 80 ° C. using an oil bath, and gradually increase the degree of vacuum so that the methanol does not bump. Distilled off to obtain polyorganosiloxane P-1 (viscosity 100 poise at 23 ° C.).

[Synthesis Example 2]
(Synthesis of polyorganosiloxane P-2)
To a 500 ml three-necked round bottom flask equipped with a water-cooled condenser and a stirring blade with a vacuum seal was added 86.52 g (0.4 mol) of diphenylsilanediol and 52.45 g (0.211 mol) of 3-methacryloyloxypropyltrimethoxysilane. , 3-morpholinopropyltrimethoxysilane 35.12 g (0.141 mol) and tetra-isopropoxytitanium 6.82 g (0.024 mol) were charged, and stirring was started. This was immersed in an oil bath, the temperature was set to 120 ° C., and heating was started from room temperature. On the way, methanol generated with the progress of the polymerization reaction was allowed to react with a water-cooled condenser while reacting until the temperature of the reaction solution became constant, and then heated and stirred for another 30 minutes.

  Then, attach a hose connected to a cold trap and a vacuum pump, stir vigorously while heating at 80 ° C. using an oil bath, and gradually increase the degree of vacuum so that the methanol does not bump. Distilled off to obtain polyorganosiloxane P-2 (viscosity 220 poise at 40 ° C.).

[Example 1]
(Preparation of photosensitive polyorganosiloxane composition C-1)
(A) 100 parts by mass of the polyorganosiloxane P-1 obtained in Synthesis Example 1 as a polyorganosiloxane, and (b) 2-benzyl-2-dimethylamino-1- ( 4 parts by mass of 4-morpholinophenyl) -butanone-1 (IRGACURE369 manufactured by Ciba Japan), (c) a nonionic surfactant S-1 represented by the following formula (7) as a nonionic surfactant 0.4 part by mass of OMNOVA Solutions brand name PolyFox product number PF-656), (d) 30 parts by mass of benzyl alcohol as a dispersion solvent as an organic solvent, 30 parts by mass of methyl-n-amyl ketone as a dispersion solvent, and others As a component, 0.4 parts by mass of 4,4′-bis (diethylamino) benzophenone, ethoxylated bisphenol A 30 parts by weight of dimethacrylate (number of ethylene glycol units: 30, NOF PDBE-1300), 30 parts by weight of 3-methacryloxypropyltrimethoxysilane, 150 parts by weight of silicone resin (SR-20, manufactured by Konishi Chemical) The mixture was mixed and filtered through a Teflon (registered trademark) filter having a pore size of 0.2 microns to obtain a varnish-like photosensitive polyorganosiloxane composition C-1.

[Example 2]
(Preparation of photosensitive polyorganosiloxane composition C-2)
The nonionic surfactant S-1 in Example 1 was the same as Example 1 except that the surfactant S-2 represented by the following formula (8) was used (trade name: PolyFox product number PF-6320 manufactured by OMNOVA Solutions). Thus, a varnish-like photosensitive polyorganosiloxane composition C-2 was obtained.

[Example 3]
(Preparation of photosensitive polyorganosiloxane composition C-3)
A varnish-like photosensitive polyorganosiloxane composition C-3 was obtained in the same manner as in Example 1, except that the dispersion solvent in Example 1 was replaced with 30 parts by mass of acetophenone and 30 parts by mass of benzyl alcohol.

[Example 4]
(Preparation of photosensitive polyorganosiloxane composition C-4)
A varnish-like photosensitive polyorganosiloxane composition C-4 was obtained in the same manner as in Example 1 except that the dispersion solvent in Example 1 was replaced with 30 parts by mass of isobutyl alcohol and 30 parts by mass of benzyl alcohol.

[Example 5]
(Preparation of photosensitive polyorganosiloxane composition C-5)
A varnish-like photosensitive polyorganosiloxane composition C-5 was obtained in the same manner as in Example 1, except that the dispersion solvent in Example 1 was replaced with 30 parts by mass of 2-octanone and 30 parts by mass of ethylene glycol monophenyl ether. It was.

[Example 6]
(Preparation of photosensitive polyorganosiloxane composition C-6)
(A) 100 parts by mass of the polyorganosiloxane P-2 obtained in Synthesis Example 2 as a polyorganosiloxane, and (b) 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1 (IRGACURE369 manufactured by Ciba Japan), (c) nonionic surfactant S-1 as a nonionic surfactant (trade name: PolyFox product number PF manufactured by OMNOVA Solutions) -656) is 0.4 parts by mass, (d) 30 parts by mass of benzyl alcohol as a dispersion solvent as an organic solvent, 30 parts by mass of methyl-n-amyl ketone as the dispersion solvent, and 4,4′- 0.4 parts by mass of bis (diethylamino) benzophenone, ethoxylated bisphenol A dimethacrylate (eth 30 parts by weight of lenglycol units 30 NOF PDBE-1300), 30 parts by weight of 3-methacryloxypropyltrimethoxysilane, and 150 parts by weight of silicone resin (217 flakes by Dow Corning) The mixture was filtered through a Teflon (registered trademark) filter having a pore size of 0.2 microns to obtain a varnish-like photosensitive polyorganosiloxane composition C-6.

[Example 7]
(Preparation of photosensitive polyorganosiloxane composition C-7)
The nonionic surfactant S-1 in Example 6 was changed to a nonionic surfactant S-3 [(hydroxyethyleneoxypropyl) methylsiloxane-dimethylsiloxane compound, Gelest product number CMS-626]. In the same manner as in Example 6, a varnish-like photosensitive polyorganosiloxane composition C-7 was obtained.

[Example 8]
(Preparation of photosensitive polyorganosiloxane composition C-8)
The nonionic surfactant S-1 in Example 6 was replaced with the nonionic surfactant S-4 [trade name Megafac product number R-08 manufactured by Dainippon Ink and Chemicals, Inc., which is a perfluoroalkyl group-containing oligomer]. A varnish-like photosensitive polyorganosiloxane composition C-8 was obtained in the same manner as in Example 6 except for changing to.

[Comparative Example 1]
(Preparation of photosensitive polyorganosiloxane composition C-9)
(D) Varnish-like photosensitivity in the same manner as in Example 1 except that 60 parts by mass of N-methyl-2-pyrrolidone was added as a diluting solvent without using an alcohol or ketone organic solvent as the organic solvent. Polyorganosiloxane composition C-9 was obtained.

  Next, the photosensitive polyorganosiloxane composition prepared in Examples and Comparative Examples of the present invention was applied to a 6-inch silicon wafer on which an organic thin film layer was formed using a spin coater (model name Clean Track Mark 7 manufactured by Tokyo Electron). 2mm width was cut from the edge of the wafer using cyclopentanone and soft-baked at 125 ° C for 12 minutes to obtain a coating film having an initial film thickness of 45 microns.

The edge cut width of the wafer outer peripheral part on which this coating film was formed was measured, and the coating property (wetting property) on the organic thin film was evaluated. The evaluation criteria are as follows.
○: Less than 2 mm from the wafer edge. There is no retraction of the coating film toward the wafer center.
X: 2 mm or more and less than 5 mm from the wafer edge. There is a slight receding coating toward the wafer center.
The results are shown in Table 1.

(Photosensitive property evaluation: pattern swelling, adhesion to substrate)
The photosensitive polyorganosiloxane composition prepared in Examples and Comparative Examples of the present invention was applied on a 6-inch silicon wafer using a spin coater (model name Clean Track Mark 7 manufactured by Tokyo Electron), and 125 ° C. for 12 minutes. Soft baking was performed to obtain a coating film having an initial film thickness of 45 microns. This coating film was exposed to an exposure dose of 100 to 900 mJ / through an evaluation photomask designed with a lattice pattern imitating a lens array protection spacer structure of a CMOS image sensor by an i-line stepper exposure machine (Nikon model name: NSR2005i8A). The exposure was performed in steps of 100 mJ / cm ² in the lateral direction in the range of cm ^{2 and} in steps of 2 microns in the longitudinal direction in the range of 16 to 32 microns. 30 minutes after exposure, propylene glycol monomethyl ether acetate was used as a developer, and the time until the unexposed area completely dissolved and disappeared was multiplied by 1.4, followed by iso-butyl alcohol. Then, a rotary spray rinsing treatment was performed for 10 seconds to obtain a grid-like relief pattern.

  The obtained relief pattern was visually observed under an optical microscope, and the pattern was swollen (◯: sharp without swelling, Δ: slightly swollen locally, x: apparently swollen), adhesion to the substrate (○: lifted) No peeling, Δ: Slightly lifted or peeled locally, ×: Full surface or clear lifted or peeled). The results are shown in Table 1.

(Low-temperature curability: Evaluation of elongation of cured film)
In the same manner as in the above-described evaluation of the photosensitive properties, the composition was applied onto a 6-inch silicon wafer by vacuum-depositing aluminum and soft-baked, and then a vertical curing furnace (manufactured by Koyo Thermo Systems, model name VF). -2000B), a heat curing treatment was performed at 180 ° C. for 2 hours under a nitrogen atmosphere, and a resin film having a thickness of 10 μm after curing was produced. This resin film is cut to a width of 3.0 mm using a dicing saw (manufactured by DISCO, model name DAD-2H / 6T), immersed in a 10% hydrochloric acid aqueous solution and peeled off from the silicon wafer, and a strip-shaped film sample. It was.

  The film sample was allowed to stand in an atmosphere of 23 ° C. and 55% relative humidity for 24 hours, and then subjected to a tensile test using a Tensilon tensile tester based on ASTM D-882-88 to evaluate the elongation of the film. The results are shown in Table 1.

  Examples of the present invention exhibit good wettability to organic thin films, excellent photosensitivity (ie lithography properties) and low temperature curability.

  Comparative Example 1 is a case where the organic solvent of the alcoholic hydroxyl group-containing compound or ketone compound, which is an essential component of the present invention, is not applied, but the wettability with respect to the organic thin film is inferior compared with the examples of the present invention, Inferior to low-temperature curability.

  The photosensitive polyorganosiloxane composition of the present invention is a semiconductor having an insulating material for electronic parts, formation of a surface protective film, interlayer insulating film, α-ray shielding film, etc. in a semiconductor device, and an image sensor, micromachine, or microactuator. It can utilize suitably as a resin composition used for an apparatus etc. and its formation.

Claims (10)

The following components (a) to (d),
(A) At least one selected from the group consisting of at least one silanol compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula (3) 100 parts by mass of a polyorganosiloxane obtained by polymerizing the alkoxysilane compound in the presence of a catalyst without adding water

(The plurality of R ₁ are each independently a group having 6 to 20 carbon atoms and containing at least one aromatic group.)

(R ₂ is an organic group having 2 to 17 carbon atoms including a group having a radical polymerizable carbon-carbon double bond, and the plurality of R ₃ are each independently a methyl group or an ethyl group.)

(R ₄ is an organic group having 2 to 17 carbon atoms which does not include a group having a radically polymerizable carbon-carbon double bond and includes at least one group having a 5- to 6-membered nitrogen atom-containing heterocyclic ring. And a plurality of R ₅ are each independently a methyl group or an ethyl group).
(B) 0.2-20 parts by mass of a photopolymerization initiator,
(C) 0.01-10 parts by mass of a nonionic surfactant, and (d) a photosensitive polysiloxane containing 10-150 parts by mass of at least one organic solvent selected from a compound having an alcoholic hydroxyl group and a ketone compound. Organosiloxane composition.   The photosensitive polyorganosiloxane composition according to claim 1, wherein the component (c) contains at least one fluorine atom. The component (c) is represented by the following general formula (4)

(R ₆ is a trifluoromethyl group or a pentafluoroethyl group, and n is an integer of 1 to 25.)
The photosensitive polyorganosiloxane composition of Claim 1 which is at least 1 sort (s) of compound shown by these. A method for forming a polyorganosiloxane cured relief pattern using the photosensitive polyorganosiloxane composition according to any one of claims 1 to 3,
Applying the photosensitive polyorganosiloxane composition on a substrate to form a coating film;
Irradiating the coating film with an actinic ray through a patterning mask and photocuring the exposed portion;
Removing a portion other than the exposed portion of the coating film using a developer;
A method comprising heating at least the coating film and heat-curing the coating film;   A polyorganosiloxane cured relief pattern obtained by the method of claim 4.   A semiconductor device comprising the polyorganosiloxane cured relief pattern according to claim 5. A crystal substrate on which an integrated circuit is formed, a microstructure formed on the crystal substrate, a package material for covering the microstructure, and a support for supporting the package material on the microstructure A spacer material,
The semiconductor device according to claim 5, wherein the polyorganosiloxane cured relief pattern is formed as the spacer material.   The semiconductor device according to claim 7, wherein the integrated circuit includes a photodiode.   The semiconductor device according to claim 7, wherein the microstructure is a microlens. A method for manufacturing a semiconductor device using the photosensitive polyorganosiloxane composition according to claim 1,
A step of coating the photosensitive polyorganosiloxane composition directly or via a thin film layer on a microstructure formed on a crystal substrate on which an integrated circuit is formed, to form a coating film;
Irradiating the coating film with an actinic ray through a patterning mask and photocuring the exposed portion;
Removing a portion other than the exposed portion of the coating film using a developer;
A method comprising heating at least the coating film and heat-curing the coating film;